Asymmetric pigment

ABSTRACT

An asymmetric pigment including a first Fabry-Perot structure; and a second Fabry-Perot structure; wherein the first Fabry-Perot structure and the second Fabry-Perot structure have a similar hue angle within +/−45 degrees is disclosed. Other asymmetric pigments are also disclosed as well as methods of making the disclosed pigments.

FIELD OF THE INVENTION

The present disclosure generally relates to asymmetric pigments that can(i) include a visible color at angle, (ii) color shift, and (iii) have asmall pigment size. Methods of making the asymmetric pigments are alsodisclosed.

BACKGROUND OF THE INVENTION

Color shifting magnetic pigments based on color by interference with anoptical thickness of 2 or 4 quarterwave thickness at the reflection peakcan be attractive from a hiding point of view because the flakes arethin. However, these flakes have a few drawbacks. In particular, thecolor at angle may not be very visible as the tilt angle required to seethis color is high. The high tilt angle results in a low lightreflection in most lighting conditions. Additionally, the flakes arehard to break into a small pigment size because the opaque magnetic coreis relatively strong in combination with a low per flake weight.

Previously, in order to achieve a strong color that is visible at a hightilt angle and easy to alter, for example into flakes, a symmetricpigment having optically thick layers was made. However, the pigmentwith the optically thicker layers was more expensive to make. In orderto minimize costs, pigments having optically thinner layers were made.However, the pigments with the optically thinner layers did not producea strong color effect and were hard to alter, for example into flakes,because they possessed a high relative metal content and a low weight tosurface ratio. Although the pigments with the optically thinner layerswere cheaper to make, they exhibited a low color and/or color shifteffect and were larger sized flakes that were visible in a colorshifting colorant.

Dual cavity design pigments can achieve colors that are not achievedwith 2 quarter wave or 4 quarter wave single cavity designs. However,production is not simple and the dual cavity design pigments arerelatively thick, heavy, and expensive.

SUMMARY OF THE INVENTION

In an aspect, there is disclosed an asymmetric pigment comprising afirst Fabry-Perot structure; and a second Fabry-Perot structure; whereinthe first Fabry-Perot structure and the second Fabry-Perot structurehave a similar hue angle within +/−45 degrees, and wherein the averagethickness of the first Fabry-Perot structure and the second Fabry-Perotstructure is a ratio of 1:1.5 to 1:2.5.

In another aspect, there is disclosed an asymmetric pigment comprising aFabry-Perot structure; and a dual cavity; wherein the Fabry-Perotstructure and the dual cavity have a similar hue angle within +/−45degrees.

In a further aspect, there is disclosed a method of forming anasymmetric pigment comprising depositing on a substrate a firstFabry-Perot structure; and depositing a second Fabry-Perot structure onthe first Fabry-Perot structure; wherein the first Fabry-Perot structureand the second Fabry-Perot structure have a similar hue angle within+/−45 degrees.

In a further aspect, there is disclosed a method for making a pigmentcomprising depositing on a substrate a Fabry-Perot structure; anddepositing a dual cavity on the Fabry-Perot structure; wherein theFabry-Perot structure and the dual cavity have a similar hue anglewithin +/−45 degrees.

In another aspect, there is disclosed a method for making a pigmentcomprising depositing on a substrate a dual cavity; and depositing aFabry-Perot structure on the dual cavity; wherein the Fabry-Perotstructure and the dual cavity have a similar hue angle within +/−45degrees.

Additional features and advantages of various embodiments will be setforth, in part, in the description that follows, and will, in part, beapparent from the description, or may be learned by the practice ofvarious embodiments. The objectives and other advantages of variousembodiments will be realized and attained by means of the elements andcombinations particularly pointed out in the description herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure in its several aspects and embodiments can bemore fully understood from the detailed description and the accompanyingdrawings, wherein:

FIG. 1 is a cross-section view of an asymmetric pigment according to anaspect of the invention;

FIG. 2A is a cross-section of a Fabry-Perot structure according to anaspect of the invention;

FIG. 2B is a cross-section of a Fabry-Perot structure according toanother aspect of the invention;

FIG. 2C is a cross-section of a Fabry-Perot structure according toanother aspect of the invention;

FIG. 3 is a cross-section view of an asymmetric pigment according toanother aspect of the invention;

FIG. 4A is a cross-section view of an asymmetric pigment according toanother aspect of the invention;

FIG. 4B is a cross-section view of an asymmetric pigment according toanother aspect of the invention;

FIG. 4C is a cross-section view of an asymmetric pigment according toanother aspect of the invention;

FIG. 5A is a cross-section of a dual cavity according to an aspect ofthe invention;

FIG. 5B is a cross section of a dual cavity according to another aspectof the invention;

FIG. 5C is a cross section of a dual cavity according to another aspectof the invention; and

FIG. 6 is an L.*a*b* graph illustrating hue angle.

Throughout this specification and figures like reference numbersidentify like elements.

DETAILED DESCRIPTION OF THE INVENTION

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory only,and are intended to provide an explanation of various embodiments of thepresent teachings.

In its broad and varied embodiments, disclosed herein are pigments 10,such as asymmetric pigments, and a method of manufacturing the pigments10. The pigments 10 can be blended with a liquid medium to form a colorshifting colorant. In an aspect, an asymmetric design may result in alower chromaticity at angle resulting in a color to dark shift. Formagnetically aligned pigments, this may be an attractive aspect becauseit may result in areas with abundant color surrounded by, or borderingto, areas that show much less color than with a symmetric pigment. Thecolored area may appear to move with a change in viewing angle.

FIGS. 1, 3, and 4A-4C illustrate various pigments 10, such as opticaldevices in the form of flakes, foils, or sheets, according to variousexamples. Although, these Figures illustrate specific layers in specificorders, one of ordinary skill in the art would appreciate that thepigment 10 can include any number of layers in any order. Additionally,the composition of any particular layer can be the same or differentfrom the composition of any other layer. It is also envisioned that thepigments 10 disclosed herein can include additional layers, such asintermediate layers or intervening layers. It is also envisioned thatthe layers of the pigments 10 may be surfaced modified, such as byoxidation. It will be appreciated that the disclosed pigments 10 can bedimensionally asymmetric, i.e., one side of the pigment can be thinner,for example can be less physically and/or optically thick, as comparedto an opposite side of the pigment 10, which can be thicker, such asphysically and/or optically.

The pigments 10 disclosed herein can provide a balance between cost andcolor effect. Namely, the pigments 10 are asymmetric having opticallythinner layers on one side, i.e., to achieve a lower cost, and havingoptically thicker layers on an opposite side, i.e., to achieve astronger color at angle effect. The asymmetric design can result in ahigher per flake weight than optically thinner symmetric flakes and canimprove breaking of the pigment into pigment flakes. In addition, acolor-shifting colorant including the pigments 10 can have a homogenousdistribution of per flake weight in order to avoid weight inducedseparation in a paint or ink vehicle either in the preparation, storageor application phase. For example, the use of the pigments 10 in a colorshifting colorant can result in a 50/50 chance of either side of thepigment 10 facing up because all of the pigments 10 present in the colorshifting colorant can have the same weight. For example, some of thepigments 10 can lay with, for example, a first Fabry-Perot structure 20side up, and some of the pigments 10 can lay with the second Fabry-Perotstructure 20′ side up. In another aspect, some of the pigments 10 canlay with the Fabry-Perot structure 20 (such as either a 2 or 4 quarterwave stack) side up, and some of the pigments 10 can lay with a dualcavity 26 side up.

The pigment 10 can be asymmetric including an optically thinner side andan optically thicker side. As shown in FIG. 1, in an aspect, the pigment10 can include a first Fabry-Perot structure 20; and a secondFabry-Perot structure 20′; wherein the first Fabry-Perot structure andthe second Fabry-Perot structure have a similar hue angle within +/−45degrees, and wherein the average thickness of the first Fabry-Perotstructure and the second Fabry-Perot structure is a ratio of 1:1.5 to1:2.5. The average thickness of the first Fabry-Perot structure and thesecond Fabry-Perot structure is a ratio of 2:2.5 to 2:3.5, for example,a ratio of 1:2.5 to 1:3.5. In another aspect, the asymmetric pigment caninclude a first Fabry-Perot structure; and a second Fabry-Perotstructure; wherein the first Fabry-Perot structure and the secondFabry-Perot structure have a similar hue angle within +/−45 degrees. AFabry-Perot structure (first 20, second 20′, third 20′″, etc.) can eachindependently include a reflector layer 14, a dielectric layer 12, andan absorber layer 18, as shown in FIGS. 2A-2C. It will be understoodthat any two Fabry-Perot structures 20 can be used in forming thepigment 10 so long as each Fabry-Perot structure 20 has a differentoptical thickness.

In an aspect, an optical thickness of each of the first Fabry-Perotstructure 20 and the second Fabry-Perot structure 20′ can be different.For example, the first Fabry-Perot structure 20 can include a 2 quarterwave optical thickness ranging from about 200 nm to about 400 nm or a 4quarter wave optical thickness ranging from about 400 nm to about 600nm. As a further example, the second Fabry-Perot structure 20 caninclude a 4 quarter wave optical thickness ranging from about 400 nm toabout 600 nm or a 6 quarter wave optical thickness ranging from about600 nm to about 800 nm.

An asymmetric pigment 10, such as shown in FIG. 1, can include a firstFabry-Perot structure 20 including a 2 quarter wave optical thicknessranging from about 200 to about 400 nm; and a second Fabry-Perotstructure 20′ including a 4 quarter wave optical thickness ranging fromabout 400 to about 600 nm.

In another aspect, an asymmetric pigment 10 can include a firstFabry-Perot structure 20′ including a 4 quarter wave optical thicknessranging from about 400 to about 600 nm; and a second Fabry-Perotstructure 20″ including a 6 quarter wave optical thickness ranging fromabout 600 to about 800 nm.

The asymmetric pigments 10 can be combined with a liquid medium to forma color shifting colorant. The color shifting colorant can be, forexample, an ink or a paint. Non-limiting examples of a liquid medium caninclude solvents, for example acetates, such as ethyl acetate, propylacetate, and butyl acetate; acetone; water; ketones, such as dimethylketone (DMK), methylethyl ketone (MEK), secbutyl methyl ketone (SBMK),ter-butyl methyl ketone (TBMK), cyclopenthanon, and anisole; glycol andglycol derivatives, such as propylene glycol methyl ether, and propyleneglycol methyl ether acetate; alcohols, such as isopropyl alcohol, anddiacetone alcohol; esters, such as malonates; heterocyclic solvents,such as n-methyl pyrrolidone; hydrocarbons, such as toluene, and xylene;coalescing solvents, such as glycol ethers; and mixtures thereof. In anaspect, the liquid medium can be present in an amount ranging from about0% to about 99.9%, for example from about 0.005% to about 99%, and as afurther example from about 0.05% to about 90% by weight relative to thetotal weight of the color shifting colorant.

Each of the disclosed exemplary pigments 10 can be altered, such asmechanically altered, for example by breaking, to form flakes, foils, orsheets. The pigments 10 can be formed into flakes, foils, or sheetsranging from about 2 microns to about 40 microns in dimension. Thepigments 10 can have a D50 (50% of pigments larger than 20 microns and50% smaller) of 20 microns, with a D0.01 (99.9% of pigments larger than4 microns) of 4 microns and a D99.99 (0.01% of pigments smaller than 80microns) of 80 microns, Pigments 10 with a small pigment size, in therange of 5 to 15 micron D50, can result in less grainy prints but thisflake size can be difficult to achieve with strong interference colorslike gold, orange, and red without using the asymmetric configurationbecause the collision impact of optically thinner, lighter weight,flakes in an aft based grinding system is lower. In an aspect, thepigments 10 can have a D50 around 11 microns and can possess stronginterference colors.

The pigments 10 can each have a similar (within plus or minus 45 degree)hue angle, for example as shown in FIG. 6. Two more distinctly differentcolors for each side of the pigment 10 resulting in a third color byadditive blending is not within the scope. It is common to make colorshifting interference pigments with a slightly different dielectricthickness on each side to allow blend control over chromaticity and hue.This is not within the scope of this invention. This minor thicknessdifference may result in a different hue angle but does notsignificantly impact the color at angle or the breaking characteristics.

In some examples, the pigment 10 can exhibit optical interference.Alternatively, in some examples, the pigment 10 cannot exhibit opticalinterference. In an aspect, the pigment 10 can exploit interference togenerate color. In another aspect, the pigment 10 cannot exploitinterference to generate color.

In a further aspect, the asymmetric pigment 10 can include amagnetic-containing layer 16 sandwiched between the first Fabry-Perotstructure 20 and the second Fabry-Perot structure 20′, as shown in FIG.3. In an aspect, a magnetic-containing layer 16 can be sandwichedbetween a second Fabry-Perot structure 20′ and a third Fabry-Perotstructure 20″ (not shown). the asymmetric pigment 10 can include amagnetic-containing layer 16 sandwiched between a Fabry-Perot structure20 and a dual cavity, as shown in FIG. 4C. As discussed more fullyherein, the reflector layer 14 and/or the absorber layer 18 can eachindependently include magnetic-containing materials, which can also actas a magnetic-containing layer 16 for any of the Fabry-Perot structures20, 20′, or 20″.

The magnetic-containing layer 16 can include magnetic permeable,magnetic orientable materials, magnetic materials, and combinationsthereof. A magnetic material, such as ferromagnetic and ferrimagneticmaterials, includes but is not limited to, nickel, cobalt, iron,gadolinium, terbium, dysprosium, erbium, and their blends, alloys oroxides. Other examples of blends or alloys include, but are not limitedto, Fe/Si, Fe/Ni, Fe/Co, Fe/Ni/Mo, Fe/Cr, Ni/Cr, and combinationsthereof. In an aspect, the magnetic-containing layer 16 can include apolymer containing iron oxide particles. Hard magnets of the type SmCo₅,NdCo₅, Sm₂Co₁₇, Nd₂Fe₁₄B, Sr₆Fe₂O₃, TbFe₂, Al—Ni—Co, and combinationsthereof, can also be used as well as spinel ferrites of the type Fe₃O₄,NiFe₂O₄, MnFe₂O₄, CoFe₂O₄, or garnets of the type YIG or GdIG, andcombinations thereof. In an aspect, the magnetic material may beferritic stainless steel. The magnetic material can be selected for itsreflecting or absorbing properties as well as its magnetic properties.The magnetic-containing layer 16 may be formed by a material havingmagnetic and non-magnetic particles, or magnetic particles withinnon-magnetic medium, for example cobalt-doped zinc oxide film depositedon a substrate. The magnetic-containing layer 16 can either be adistinct layer or can either function as a reflector layer 14 or anabsorber layer 18.

Although this broad range of magnetic materials can be used, “soft”magnets can be used in an aspect. As used herein, the term “softmagnets” refers to any material exhibiting ferromagnetic properties buthaving a remanence that is substantially zero after exposure to amagnetic force. Soft magnets can show a quick response to an appliedmagnetic field, but have very low (coercive fields (Hc)=0.05-300 Oersted(Oe)) or zero magnetic signatures, or retain very low magnetic lines offorce after the magnetic field is removed. Similarly, as used herein,the term “hard magnets” (also called permanent magnets) refers to anymaterial that exhibits ferromagnetic properties and that has a longlasting remanence after exposure to a magnetizing force. A ferromagneticmaterial is any material that has permeability substantially greaterthan 1 and that exhibits magnetic hysteresis properties. In an aspect,any magnetic material can be used in the magnetic-containing layer 16 solong as the material enables the orienting of the pigment 10 in amagnetic field.

The magnetic-containing layer 16 can have a thickness ranging from about10 nm to about 100 nm, for example from about 35 nm to about 45 nm, andas a further example from about 40 nm. The magnetic-containing layer 16can be deposited to a thickness so that it is substantially opaque. Inan aspect, the magnetic-containing layer 16 can be deposited to athickness so that it is not substantially opaque.

The magnetic-containing layer 16 can be formed using conventionaldeposition processes, such as physical vapor deposition techniques; aswell as sputtering including magnetron sputtering; thermal evaporation;electron beam evaporation; and cathodic arc evaporation. In an aspect,the magnetic-containing layer 16 can also be formed using a liquidcoating process.

In another aspect, the asymmetric pigment 10 can include a Fabry-Perotstructure 20 and a dual cavity 26, as shown in FIGS. 4A-4C, wherein theFabry-Perot structure and the dual cavity have a similar hue anglewithin +/−45 degrees. The Fabry-Perot structure 20 can be as describedin relation to FIGS. 1 and 2A-2C.

The dual cavity 26 can include a reflector layer 14, and a stack ofalternating dielectric layers 12 and absorber layers 18, as shown inFIGS. 5A-5C. For example, the stack of alternating dielectric layers 12and absorber layers 18 can include a first dielectric layer 12, a firstabsorber layer 18, a second dielectric layer 12′, and a second absorberlayer 18′. The stack of alternating dielectric layers 12 and absorberlayers 18 can include any number of each layer.

The first dielectric layer 12 can include a quarter wave opticalthickness chosen from a 2 quarter wave optical thickness, a 4 quarterwave optical thickness, and a 6 quarter wave optical thickness. Thesecond dielectric layer 12′ can include a quarter wave optical thicknesschosen from a 2 quarter wave optical thickness, a 4 quarter wave opticalthickness, and a 6 quarter wave optical thickness.

As shown in FIG. 5A, the dual cavity 26 can include a first dielectriclayer 12 having a 2 quarter wave optical thickness ranging from about200 to about 400 nm; and a second dielectric layer 12′ having 2 quarterwave optical thickness ranging from about 200 to about 400 nm. Inanother aspect, as shown in FIG. 5B, the dual cavity 26 can include afirst dielectric layer 12 having a 2 quarter wave optical thicknessranging from about 200 to about 400 nm; and a second dielectric layer12′ having 4 quarter wave optical thickness ranging from about 400 toabout 600 nm. In a further aspect, as shown in FIG. 5C, the dual cavity26 can include a first dielectric layer 12 having a 4 quarter waveoptical thickness ranging from about 400 to about 600 nm; and a seconddielectric layer 12′ having 6 quarter wave optical thickness rangingfrom about 600 to about 800 nm.

The reflector layer 14 of the Fabry-Perot structure 20 and/or the dualcavity 26 can be a wideband reflector, e.g., spectral and Lambertianreflector (e.g., white TiO₂). The reflector layer 14 can eachindependently include metals, non-metals, and/or metal blends or alloys.The terms “metallic” or “metallic layer” used herein, unless otherwisestated, are intended to include all metals, metal blends and alloys,pure metal or metal alloy containing materials, compound, compositions,and/or layers.

In one example, the materials for the reflector layer 14 can include anymaterials that have reflective characteristics in the desired spectralrange. For example, any material with a reflectance ranging from 50% to100% in the desired spectral range. An example of a reflective materialcan be aluminum, which has good reflectance characteristics, isinexpensive, and easy to form into or deposit as a thin layer. Othermaterials can also be used in place of aluminum. For example, copper,silver, gold, platinum, palladium, nickel, cobalt, niobium, chromium,tin, and combinations, blends or alloys of these or other metals can beused as reflective materials. In an aspect, the material for thereflector layer 14 can be a white or light colored metal. In otherexamples, the reflector layer 14 can include, but is not limited to, thetransition and lanthanide metals and combinations thereof; as well asmetal carbides, metal oxides, metal nitrides, metal sulfides, acombination thereof, or mixtures of metals and one or more of thesematerials.

The thickness of the reflector layer 14 can range from about 5 nm toabout 5000 nm, although this range should not be taken as restrictive.For example, the lower thickness can be selected so that the reflectorlayer 14 provides a maximum transmittance of 0.8. Additionally, oralternatively, for a reflector layer 14 including aluminum the minimumoptical density (OD) can be from about 0.1 to about 4 at a wavelength ofabout 550 nm.

In order to obtain a sufficient optical density and/or achieve a desiredeffect, a higher or lower minimum thicknesses can be required dependingupon the composition of the reflector layer 14. In some examples, theupper limit can be about 5000 nm, about 4000 nm, about 3000 nm, about1500 nm, about 200 nm, and/or about 100 nm. In one aspect, the thicknessof the reflector layer 14 can range from about 10 nm to about 5000 nmfor example, from about 15 nm to about 4000 nm, from about 20 nm toabout 3000 nm, from about 25 nm to about 2000 nm, from about 30 nm toabout 1000 nm, from about 40 nm to about 750 nm, or from about 50 nm toabout 500 nm, such as from about 60 nm to about 250 nm or from about 70nm to about 200 nm.

In one aspect, the dielectric layer 12 of the Fabry-Perot structure 20and/or the dual cavity 26 can be disposed on the reflector layer 14. Thedielectric layer 12 can have a refractive index of greater or less thanabout 1.5. For example, the dielectric layer 12 can have a refractiveindex of approximately 1.5. The refractive index of a dielectric layer12 can be selected to provide a degree of color travel required whereincolor travel can be defined as the change in hue angle measured inL*a*b* color space with the viewing angle.

The optical thickness is a well-known optical parameter defined as theproduct ηd, where η is the refractive index of the layer and d is thephysical thickness of the layer. Typically, the optical thickness of alayer is expressed in terms of a quarter wave optical thickness (QWOT)that is equal to 4ηd/λ, where λ is the wavelength at which a QWOTcondition occurs. The optical thickness of dielectric layer 12 can rangefrom about 2 QWOT at a design wavelength of about 200 nm to about 9 QWOTat a design wavelength of about 700 nm, and for example 2-6 QWOT at200-800 nm, depending upon the color shift desired. Suitable materialsfor dielectric layer 12 include those having a “high” index ofrefraction, defined herein as greater than about 1.65, as well as thosehave a “low” index of refraction, which is defined herein as about 1.65or less. For the purpose of this specification the qualification 2, 4 or6 quarter wave qualification is made based on FIG. 6 that plots hueangle at normal angle versus dielectric thickness. As an example a goldcolor (around 90 degree hue angle) is achieved at an optical thicknessof 140 nm (2 quarter wave), 280 nm (4 quarter wave) and 430 nm (6quarter wave). Some of the colors achieved with specific quarter wavecounts are less attractive for the human eye due to low chromaticity orlow lightness but most colors in the visible spectrum can be made withat least 2 quarter wave counts. At more than 2 quarter waves, multiplereflection peaks fit in the visible spectrum and this impacts thechromaticity at specific hue angles. A 2 quarter wave green has a verylow chromaticity and this color is usually made as either a 4 or a 6quarter wave stack. A 6 quarter wave green has a reflection peak in theblue and will therefore have a higher chromaticity when made as ablue-ish green. Magenta or red works well as a 2 or a 4 quarter wavestack, yet not as well as a 6 quarter wave stack as it has anunattractive low lightness.

Examples of suitable high refractive index materials for dielectriclayer 12 include zinc sulfide (ZnS), zinc oxide (ZnO), zirconium oxide(ZrO₂), titanium dioxide (TiO₂), carbon (C), indium oxide (In₂O₃),indium-tin-oxide (ITO), tantalum pentoxide (Ta₂O₅), ceric oxide (CeO₂),yttrium oxide (Y₂O₃), europium oxide (Eu₂O₃), iron oxides such as (II)diiron (III) oxide (Fe₃O₄) and ferric oxide (Fe₂O₃), hafnium nitride(HfN), hafnium carbide (HfC), hafnium oxide (HfO₂), lanthanum oxide(La₂O₃), magnesium oxide (MgO), neodymium oxide (Nd₂O₃), praseodymiumoxide (Pr₆O₁₁), samarium oxide (Sm₂O₃), antimony trioxide (Sb₂O₃),silicon carbide (SiC), silicon nitride (Si₃N₄), silicon monoxide (SiO),selenium trioxide (Se₂O₃), tin oxide (SnO₂), tungsten trioxide (WO₃),combinations thereof, and the like.

Suitable low refractive index materials for dielectric layer 12 includesilicon dioxide (SiO₂), aluminum oxide (Al₂O₃), metal fluorides such asmagnesium fluoride (MgF₂), aluminum fluoride (AlF₃), cerium fluoride(CeF₃), lanthanum fluoride (LaF₃), sodium aluminum fluorides (e.g.,Na₃AlF₆ or Na₅Al₃F₁₄), neodymium fluoride (NdF₃), samarium fluoride(SmF₃), barium fluoride (BaF₂), calcium fluoride (CaF₂), lithiumfluoride (LiF), combinations thereof, or any other low index materialhaving an index of refraction of about 1.65 or less. For example,organic monomers and polymers can be utilized as low index materials,including dienes or alkenes such as acrylates (e.g., methacrylate),perfluoroalkenes, polytetrafluoroethylene (Teflon), fluorinated ethylenepropylene (FEP), combinations thereof, and the like.

The dielectric layer 12 can be deposited or printed or otherwise coatedas a dielectric stack having a predetermined number of layers. In thisexample, the stack can include one or more layers of a low refractiveindex material and one or more layers of a high refractive indexmaterial. The layers having low refractive index material (lowrefractive index layers) and the layers having high refractive indexmaterial (high refractive index layers) can alternate. For example, ahigh refractive index layer can be deposited or printed on the reflectorlayer 14. A low refractive index layer can then be deposited on itscorresponding high refractive index layer. This process can be repeatedas many times as necessary to create a dielectric layer 12. Thealternating layers can be stacked in any sequence, for example, thelayers can be stacked in a sequence of (H/L)_(n), (H/L)_(n)H, orL(H/L)_(n) wherein H denotes higher refractive index layer and L denotesa lower refractive index layer. The number of alternating low refractiveindex layers and the high refractive index layers (n) can range fromabout 2 to over about 75, such as from about 10 to about 50 alternatinglayers, or for example from about 5 to about 25 alternating layers. Inone aspect, the dielectric stack can comprise liquid coating printedlayers alternating in composition that increase the effective refractiveindex in another layer. Any number of layers can be printed using anynumber of different materials. In this manner, the tailoring the opticaldesign is possible by controlling the layer thickness and refractiveindex of each dielectric layer 12.

In each aspect, the dielectric layer 12 can be a transparent layer orcan be a colored layer. The performance of the dielectric layer 12 canbe determined based upon the selection of materials present in thedielectric layer 12. It is believed that the dielectric layer 12 canachieve high performance in transmission, reflection, and absorption oflight based upon the composition of the dielectric layer 12. In anaspect, the dielectric layer 12 can include a composition that allowsfor a wider range of materials configured to increase the control of theoptical performance of the dielectric layer 12. In an aspect, thedielectric layer 12 can improve at least one of the followingproperties: flake handling, corrosion, alignment, and environmentalperformance of a metal layer.

The dielectric layer can have a nominal optical thickness ranging fromabout 130 nm to about 450 nm. The thickness of the dielectric layer 12can be used to determine the overall color. When deviations from thenominal optical thickness vary too much, different areas or flakes havea different or even complementary color and when blended, a loss ofchromaticity is observed.

The absorber layer 18 can be disposed on the dielectric layer 12. Theabsorber layer 18 can independently include metals, non-metals, or metalblends or alloys. In one example, the materials for the absorber layer18 can include any absorber material, including both selective absorbingmaterials and nonselective absorbing materials. For example, theabsorber layer 18 can be formed of nonselective absorbing metallicmaterials deposited to a thickness at which the layer is at leastpartially absorbing, or semi-opaque. An example of a non-selectiveabsorbing material can be a gray metal, such as chrome or nickel. Anexample of a selective absorbing material can be copper or gold. In anaspect, the absorbing material can be chromium. Non-limiting examples ofsuitable absorber materials include metallic absorbers such as chromium,aluminum, silver, nickel, palladium, platinum, titanium, vanadium,cobalt, iron, tin, tungsten, molybdenum, rhodium, niobium, copper, aswell as other absorbers such as carbon, graphite, silicon, germanium,cermet, ferric oxide or other metal oxides, metals mixed in a dielectricmatrix, and other substances that are capable of acting as a uniform orselective absorber in the visible spectrum. Various combinations,mixtures, compounds, or alloys of the above absorber materials that maybe used to form the absorber layer 18.

Examples of suitable alloys of the above absorber materials can includeInconel (Ni—Cr—Fe), stainless steels, Hastalloys (Ni—Mo—Fe; Ni—Mo—Fe—Cr;Ni—Si—Cu) and titanium-based alloys, such as titanium mixed with carbon(Ti/C), titanium mixed with tungsten (Ti/W), titanium mixed with niobium(Ti/Nb), and titanium mixed with silicon (Ti/Si), and combinationsthereof. Other examples of suitable compounds for the absorber layer 18include, but are not limited to, titanium-based compounds such astitanium silicide (TiSi2), titanium boride (TiB2), and combinationsthereof. Alternatively, the absorber layer 18 can be composed of atitanium-based alloy deposited in a matrix of Ti, or can be composed ofTi deposited in a matrix of a titanium-based alloy or blend. Forexample, the absorber layer 18 can include chromium.

The absorber layer 18 can also be formed of a magnetic material, such asa cobalt nickel alloy or blend or an Iron Chrome alloy or blend. Thiscan simplify the manufacture of a magnetic color shifting device orstructure by reducing the number of materials required.

The absorber layer 18 can be formed to have a physical thickness in therange from about 1 nm to about 50 nm, such as from about 5 nm to about10 nm, depending upon the optical constants of the absorber layermaterial and the desired peak shift. The absorber layer 18 can becomposed of the same material or a different material if more than oneabsorber layer 18 is present in a pigment 10, such as shown in FIG. 5C,and can have the same or different physical thickness for each layer.

There is also a disclosed a method for manufacturing a pigment 10, asdescribed herein. The method can comprise depositing on a substrate afirst Fabry-Perot structure 20; and depositing on the first Fabry-Perotstructure 20 a second Fabry-Perot structure 20′. In another aspect, themethod can include depositing on a substrate a second Fabry-Perotstructure 20′; and depositing on the second Fabry-Perot structure 20′ afirst Fabry-Perot structure 20.

In another aspect, the method for manufacturing a pigment 10 cancomprise depositing a dual cavity 26 on a substrate; and depositing aFabry-Perot structure 20 on the dual cavity 26. In another aspect, themethod for manufacturing a pigment 10 can comprise depositing aFabry-Perot structure 20 on a substrate; and depositing a dual cavity 26on the Fabry-Perot structure 20.

The substrate can be made of a flexible material. The substrate can beany suitable material that can receive the deposited layers.Non-limiting examples of suitable substrate materials include polymerweb, such as polyethylene terephthalate (PET), glass, silicon wafers,etc. The substrate can include a release layer.

Any or all of the layers of the pigment 10 can be deposited onto thesubstrate by conventional deposition processes, such as physical vapordeposition, chemical vapor deposition, thin-film deposition, atomiclayer deposition, etc., including modified techniques such as plasmaenhanced and fluidized bed. One or more of the layers can be depositedusing a liquid coating process using, for example a slot die apparatus.The liquid coating process includes, but is not limited to: slot-bead,slide bead, slot curtain, slide curtain, in single and multilayercoating, tensioned web slot, gravure, roll coating, and other liquidcoating and printing processes that apply a liquid on to a substrate toform a liquid layer or film that is subsequently dried and/or cured. Theliquid coating process can allow for the transfer of the composition ata faster rate as compared to other deposition techniques, such as vapordeposition.

The substrate can then be released from the deposited layers to createthe pigment 10, for example as shown in FIGS. 1, 3 and 4A-4C. In anaspect, the substrate can be cooled to embrittle an associated releaselayer. In another aspect, the release layer could be embrittled forexample by heating and/or curing with photonic or e-beam energy, toincrease the degree of cross-linking, which would enable stripping. Thedeposited layers can then be stripped mechanically, such as by sharpbending or brushing of the surface. The released and stripped layers canbe sized into pigment 10, such as an optical device in the form of aflake, foil, or sheet, using known techniques.

In another aspect, the deposited layers can be transferred from thesubstrate to another surface. The deposited layers can be punched or cutto produce large flakes with well-defined sizes and shapes.

There is also disclosed a method for forming an asymmetric pigmentcomprising: depositing on a substrate a first Fabry-Perot structure; anddepositing a second Fabry-Perot structure on the first Fabry-Perotstructure; wherein the first Fabry-Perot structure and the secondFabry-Perot structure have a similar hue angle within +/−45 degrees.

There is also disclosed a method for making a pigment comprising:depositing on a substrate a Fabry-Perot structure; and depositing a dualcavity on the Fabry-Perot structure; wherein the Fabry-Perot structureand the dual cavity have a similar hue angle within +/−45 degrees.

There is also disclosed a method for making a pigment comprising:depositing on a substrate a dual cavity; and depositing a Fabry-Perotstructure on the dual cavity; wherein the Fabry-Perot structure and thedual cavity have a similar hue angle within +/−45 degrees.

From the foregoing description, those skilled in the art can appreciatethat the present teachings can be implemented in a variety of forms.Therefore, while these teachings have been described in connection withparticular embodiments and examples thereof, the true scope of thepresent teachings should not be so limited. Various changes andmodifications may be made without departing from the scope of theteachings herein.

This scope disclosure is to be broadly construed. It is intended thatthis disclosure disclose equivalents, means, systems and methods toachieve the devices, activities and mechanical actions disclosed herein.For each device, pigment, method, mean, mechanical element or mechanismdisclosed, it is intended that this disclosure also encompass in itsdisclosure and teaches equivalents, means, systems and methods forpracticing the many aspects, mechanisms and devices disclosed herein.Additionally, this disclosure regards a coating and its many aspects,features and elements. Such a device can be dynamic in its use andoperation, this disclosure is intended to encompass the equivalents,means, systems and methods of the use of the device and/or pigment ofmanufacture and its many aspects consistent with the description andspirit of the operations and functions disclosed herein. The claims ofthis application are likewise to be broadly construed.

The description of the inventions herein in their many embodiments ismerely exemplary in nature and, thus, variations that do not depart fromthe gist of the invention are intended to be within the scope of theinvention. Such variations are not to be regarded as a departure fromthe spirit and scope of the invention.

1-20. (canceled)
 21. An asymmetric pigment, comprising: a firstFabry-Perot structure including a first dielectric layer; and a secondFabry-Perot structure including a second dielectric layer; wherein thefirst Fabry-Perot structure has a physical thickness different from aphysical thickness of second Fabry-Perot structure.
 22. The asymmetricpigment of claim 21, further comprising a magnetic-containing layerbetween the first Fabry-Perot structure and the second Fabry-Perotstructure.
 23. The asymmetric pigment of claim 21, wherein at least oneof the first dielectric layer and the second layer includes a highrefractive index material.
 24. The asymmetric pigment of claim 23,wherein the high refractive index material is chosen from zinc sulfide,zinc oxide, zirconium oxide, titanium dioxide, carbon, indium oxide,indium-tin-oxide, tantalum pentoxide, ceric oxide, yttrium oxide,europium oxide, iron oxides, ferric oxide, hafnium nitride, hafniumcarbide, hafnium oxide, lanthanum oxide, magnesium oxide, neodymiumoxide, praseodymium oxide, samarium oxide, antimony trioxide, siliconcarbide, silicon nitride, silicon monoxide, selenium trioxide, tinoxide, tungsten trioxide, and combinations thereof.
 25. The asymmetricpigment of claim 21, wherein at least one of the first dielectric layerand the second layer includes a low refractive index material.
 26. Theasymmetric pigment of claim 25, wherein the low refractive indexmaterial is chosen from silicon dioxide, aluminum oxide, magnesiumfluoride, aluminum fluoride, cerium fluoride, lanthanum fluoride, sodiumaluminum fluorides, neodymium fluoride, samarium fluoride, bariumfluoride, calcium fluoride, lithium fluoride, combinations thereof. 27.The asymmetric pigment of claim 21, wherein at least one of the firstdielectric layer and the second dielectric layer includes magnesiumfluoride.
 28. The asymmetric pigment of claim 21, wherein at least oneof the first dielectric layer and the second dielectric layer is adielectric stack.
 29. The asymmetric pigment of claim 21, wherein atleast one of the first dielectric layer and the second dielectric layeris transparent layer.
 30. The asymmetric pigment of claim 21, wherein atleast one of the first dielectric layer and the second dielectric layeris a colored layer.
 31. The asymmetric pigment of claim 21, wherein theasymmetric pigment has a D50 of 20 microns.
 32. An asymmetric pigment,comprising: a first Fabry-Perot structure including a first dielectriclayer; and a second Fabry-Perot structure including a second dielectriclayer; wherein the first Fabry-Perot structure has an optical thicknessdifferent from an optical thickness of the second Fabry-Perot structure.33. The asymmetric pigment of claim 32, wherein the first Fabry-Perotstructure includes a 2 quarter wave optical thickness ranging from about200 to about 400 nm.
 34. The asymmetric pigment of claim 32, wherein thefirst and the second Fabry-Perot structure can each independentlyinclude a 4 quarter wave optical thickness ranging from about 400 toabout 600 nm.
 35. The asymmetric pigment of claim 32, wherein the secondFabry-Perot structure includes a 6 quarter wave optical thicknessranging from about 600 to about 800 nm.
 36. A method for manufacturingan asymmetric pigment, comprising: depositing on a substrate a firstFabry-Perot structure; and depositing on the first Fabry-Perot structurea second Fabry-Perot structure, wherein the first Fabry-Perot structurehas a physical thickness different from a physical thickness of secondFabry-Perot structure.
 37. The method of claim 36, further comprising,releasing the substrate from the deposited Fabry-Perot structures toform an asymmetric pigment.
 38. A color shifting colorant, comprising:the asymmetric pigment of claim 21, and a liquid medium.
 39. Thecolor-shifting colorant of claim 38, wherein the asymmetric pigment ishomogenously distributed in the liquid medium.
 40. A color shiftingcolorant, comprising: the asymmetric pigment of claim 32, and a liquidmedium.